|Publication number||US7554144 B2|
|Application number||US 11/279,945|
|Publication date||Jun 30, 2009|
|Filing date||Apr 17, 2006|
|Priority date||Apr 17, 2006|
|Also published as||US7972893, US20070241371, US20090239358|
|Publication number||11279945, 279945, US 7554144 B2, US 7554144B2, US-B2-7554144, US7554144 B2, US7554144B2|
|Inventors||Erh-Kun Lai, ChiaHua Ho, Kuang Yeu Hsieh|
|Original Assignee||Macronix International Co., Ltd.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (108), Non-Patent Citations (46), Referenced by (11), Classifications (21), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
1. Field of the Invention
The present invention relates to high density memory devices based on memory materials, for example resistor random access memory (RRAM) devices, the memory material switchable between electrical property states by the application of energy. The memory materials may be phase change based memory materials, including chalcogenide based materials and other materials, and to methods for manufacturing such devices.
2. Description of Related Art
Phase change based memory materials are widely used in read-write optical disks. These materials have at least two solid phases, including for example a generally amorphous solid phase and a generally crystalline solid phase. Laser pulses are used in read-write optical disks to switch between phases and to read the optical properties of the material after the phase change.
Phase change based memory materials, like chalcogenide based materials and similar materials, also can be caused to change phase by application of electrical current at levels suitable for implementation in integrated circuits. The generally amorphous state is characterized by higher resistivity than the generally crystalline state; this difference in resistance can be readily sensed to indicate data. These properties have generated interest in using programmable resistive material to form nonvolatile memory circuits, which can be read and written with random access.
The change from the amorphous to the crystalline state is generally a lower current operation. The change from crystalline to amorphous, referred to as reset herein, is generally a higher current operation, which includes a short high current density pulse to melt or breakdown the crystalline structure, after which the phase change material cools quickly, quenching the phase change process, allowing at least a portion of the phase change structure to stabilize in the amorphous state. It is desirable to minimize the magnitude of the reset current used to cause transition of phase change material from crystalline state to amorphous state. The magnitude of the reset current needed for reset can be reduced by reducing the size of the phase change material element in the cell and by reducing the size of the contact area between electrodes and the phase change material, so that higher current densities are achieved with small absolute current values through the phase change material element.
One direction of development has been toward forming small pores in an integrated circuit structure, and using small quantities of programmable resistive material to fill the small pores. Patents illustrating development toward small pores include: Ovshinsky, “Multibit Single Cell Memory Element Having Tapered Contact,” U.S. Pat. No. 5,687,112, issued Nov. 11, 1997; Zahorik et al., “Method of Making Chalogenide [sic] Memory Device,” U.S. Pat. No. 5,789,277, issued Aug. 4, 1998; Doan et al., “Controllable Ovonic Phase-Change Semiconductor Memory Device and Methods of Fabricating the Same,” U.S. Pat. No. 6,150,253, issued Nov. 21, 2000.
Problems have arisen in manufacturing such devices with very small dimensions, and with variations in process that meet tight specifications needed for large-scale memory devices. It is desirable therefore to provide a memory cell structure having small dimensions and low reset currents, and a method for manufacturing such structure.
A first aspect of the invention is directed to a memory device comprising first and second electrodes having first and second outer surfaces. The memory device also comprises an electrode-separating, insulating member between the first and second electrodes. The insulating member comprises upwardly and inwardly tapering surfaces connected by a surface segment. The surface segment has a length between the tapering surfaces near the first and second outer surfaces. The memory device also comprises a bridge across the surface segment of the insulating member. The bridge contacts the first and second outer surfaces and defines an inter-electrode path between the first and second electrodes and across the insulating member. The inter-electrode path has a path length defined at least in part by the length of the surface segment. The bridge comprises memory material switchable between electrical property states by the application of energy. In some embodiments the bridge comprises a phase change material. The insulating member may comprise an outer portion, the outer portion comprising a high density plasma-deposited separation material.
A second aspect of the invention is directed to a method for making a memory device of the type including a bridge-type memory material element switchable between electrical property states by the application of energy. An electrode structure, comprising first and second electrode elements separated by a separation material, is formed. A dielectric material is deposited onto an end surface of the separation material using a high density plasma (HDP) deposition procedure. The deposition of the dielectric material is controlled to create a dielectric material cap on the end surface, the dielectric material cap having upwardly and inwardly tapering surfaces. An electrically conductive material is deposited to contact the electrode elements and to extend along the tapering sides of the dielectric material thus creating first and second electrodes. The electrically conductive material and the dielectric material cap are planarized to create first and second outer surfaces on the first and second electrodes and a surface segment on the dielectric material. The surface segment connects the tapering sides and has a length measured between the tapering sides. At least one of the dielectric material depositing step and the planarizing step is controlled so that the length is within a chosen dimensional range. A bridge-type memory material element is formed over the surface segment and in electrical contact with portions of the first and second outer surfaces. Energy passing along an inter-electrode path between the first and second electrodes and across the surface segment of the dielectric member is concentrated within the memory material element so to facilitate changing an electrical property state of the memory material element.
The method described herein for formation of a memory cell device and, for example, in an RRAM device, can be used to make small phase change gates, bridges or similar structures for other devices.
Various features and advantages of the invention will appear from the following description in which the preferred embodiments have been set forth in detail in conjunction with the accompanying drawings.
The following description of the invention will typically be with reference to specific structural embodiments and methods. It is to be understood that there is no intention to limit the invention to the specifically disclosed embodiments and methods but that the invention may be practiced using other features, elements, methods and embodiments. Like elements in various embodiments are commonly referred to with like reference numerals.
During HDP CVD deposition both deposition and etching occurs to create the characteristic triangular shape with upwardly and inwardly tapering surfaces. General information on the HDP process can be found in the textbook “Introduction to Semiconductor Manufacturing Technology” in chapter 10 Section 7 (10.7).
One recipe that can be used to control the ratio of deposition to etching during the HDP CVD process to achieve the desired height, shape and taper angles is as follows.
Tapering surfaces 28 are illustrated as straight lines in
The dielectric material 50 covering lower electrode elements 18 is etched to expose the lower electrode elements 18. This is preferably accomplished using a slightly anisotropic etch procedure.
Thereafter memory material element 32, see
One of the advantages of the present invention is that the current needed to, for example, change the resistance of memory material element 32 at central region 38 is reduced because the volume of phase change material in the central, active region is very small. The invention facilitates scaling so that the process should work as critical dimensions on chips shrink.
Another advantage of the invention is that two of the dimensions for memory material element 32, that is length 56 and the thickness (measured in the vertical direction in the figures) of element 32, are not dependent upon lithographic techniques. In addition, while the location of and length of memory material element 32 are typically determined by lithographic techniques, neither is critical because the amount of overlap between memory material 32 and surface 34 of the electrodes can vary within a relatively wide range of distances.
The length 56 of surface segment 30 is not pattern defined, that is not defined by photolithography, and not by etch selectivity, as in the sidewall methods. Rather, length 56 is defined by the CMP process, and the control over the stop point of the CMP.
Upper electrode elements 20 in the illustrated embodiment are preferably made of TiN. Although other materials, such as TaN, TiAlN or TaAlN, may be used for upper electrode elements 20, TiN is presently preferred because it makes good contact with CST as memory material element 32, it is a common material used in semiconductor manufacturing, and it provides a good diffusion barrier at the higher temperatures at which GST-type of memory material transitions, typically in the 600-700° C. range.
Embodiments of memory device 10 include phase change based memory materials, including chalcogenide based materials and other materials, for memory material element 32. Chalcogens include any of the four elements oxygen (O), sulfur (S), selenium (Se), and tellurium (Te), forming part of group VI of the periodic table. Chalcogenides comprise compounds of a chalcogen with a more electropositive element or radical. Chalcogenide alloys comprise combinations of chalcogenides with other materials such as transition metals. A chalcogenide alloy usually contains one or more elements from column six of the periodic table of elements, such as germanium (Ge) and tin (Sn). Often, chalcogenide alloys include combinations including one or more of antimony (Sb), gallium (Ga), indium (In), and silver (Ag). Many phase change based memory materials have been described in technical literature, including alloys of: Ga/Sb, In/Sb, In/Se, Sb/Te, Ge/Te, Ge/Sb/Te, In/Sb/Te, Ga/Se/Te, Sn/Sb/Te, In/Sb/Ge, Ag/In/Sb/Te, Ge/Sn/Sb/Te, Ge/Sb/Se/Te and Te/Ge/Sb/S. In the family of Ge/Sb/Te alloys, a wide range of alloy compositions may be workable. The compositions can be characterized as TeaGebSb100−(a+b).
One researcher has described the most useful alloys as having an average concentration of Te in the deposited materials well below 70%, typically below about 60% and ranged in general from as low as about 23% up to about 58% Te and most preferably about 48% to 58% Te. Concentrations of Ge were above about 5% and ranged from a low of about 8% to about 30% average in the material, remaining generally below 50%. Most preferably, concentrations of Ge ranged from about 8% to about 40%. The remainder of the principal constituent elements in this composition was Sb. These percentages are atomic percentages that total 100% of the atoms of the constituent elements. (Ovshinsky '112 patent, columns 10-11.) Particular alloys evaluated by another researcher include Ge2Sb2Te5, GeSb2Te4 and GeSb4Te7. (Noboru Yamada, “Potential of Ge—Sb—Te Phase-Change Optical Disks for High-Data-Rate Recording”, SPIE v. 3109, pp. 28-37 (1997).) More generally, a transition metal such as chromium (Cr), iron (Fe), nickel (Ni), niobium Nb), palladium (Pd), platinum (Pt) and mixtures or alloys thereof may be combined with Ge/Sb/Te to form a phase change alloy that has programmable resistive properties. Specific examples of memory materials that may be useful are given in Ovshinsky '112 at columns 11-13, which examples are hereby incorporated by reference.
Phase change alloys are capable of being switched between a first structural state in which the material is in a generally amorphous solid phase, and a second structural state in which the material is in a generally crystalline solid phase in its local order in the active channel region of the cell. These alloys are at least bistable. The term amorphous is used to refer to a relatively less ordered structure, more disordered than a single crystal, which has the detectable characteristics such as higher electrical resistivity than the crystalline phase. The term crystalline is used to refer to a relatively more ordered structure, more ordered than in an amorphous structure, which has detectable characteristics such as lower electrical resistivity than the amorphous phase. Typically, phase change materials may be electrically switched between different detectable states of local order across the spectrum between completely amorphous and completely crystalline states. Other material characteristics affected by the change between amorphous and crystalline phases include atomic order, free electron density and activation energy. The material may be switched either into different solid phases or into mixtures of two or more solid phases, providing a gray scale between completely amorphous and completely crystalline states. The electrical properties in the material may vary accordingly.
Phase change alloys can be changed from one phase state to another by application of electrical pulses. It has been observed that a shorter, higher amplitude pulse tends to change the phase change material to a generally amorphous state. A longer, lower amplitude pulse tends to change the phase change material to a generally crystalline state. The energy in a shorter, higher amplitude pulse is high enough to allow for bonds of the crystalline structure to be broken and short enough to prevent the atoms from realigning into a crystalline state. Appropriate profiles for pulses can be determined, without undue experimentation, specifically adapted to a particular phase change alloy. A material useful for implementation of an RRAM device described herein is Ge2Sb2Te5, commonly referred to as GST. Other types of phase change materials can also be used.
The invention has been described with reference to phase change materials. However, other memory materials, also sometimes referred to as programmable materials, can also be used. As used in this application, memory materials are those materials having electrical properties, such as resistance, that can be changed by the application of energy; the change can be a stepwise change or a continuous change or a combination thereof. Other programmable resistive memory materials may be used in other embodiments of the invention, including N2 doped GST, GexSby, or other material that uses different crystal phase changes to determine resistance; PrxCayMnO3, PrSrMnO, ZrOx, or other material that uses an electrical pulse to change the resistance state; 7,7,8,8-tetracyanoquinodimethane (TCNQ), methanoflillerene 6,6-phenyl C61-butyric acid methyl ester (PCBM), TCNQ-PCBM, Cu-TCNQ, Ag-TCNQ, C60-TCNQ, TCNQ doped with other metal, or any other polymer material that has bistable or multi-stable resistance state controlled by an electrical pulse. Further examples of programmable resistive memory materials include GeSbTe, GeSb, NiO, Nb—SrTiO3, Ag—GeTe, PrCaMnO, ZnO, Nb2O5, Cr—SrTiO3.
The following are short summaries describing four types of resistive memory materials.
1. Challecogenide Material
Or other compositions with x: 0˜5; y: 0˜5; z: 0˜10
GeSbTe with doping, such as N—, Si—, Ti—, or other element doping may also be used.
Formation method: By PVD sputtering or magnetron-sputtering method with reactive gases of Ar, N2, and/or He, etc @ the pressure of 1 mtorr˜100 mtorr. The deposition is usually done at room temperature. The collimater with aspect ratio of 1˜5 can be used to improve the fill-in performance. To improve the fill-in performance, the DC bias of several ten to several hundred volts is also used. On the other hand, the combination of DC bias and the collimater can be used simultaneously.
The post deposition annealing treatment with vacuum or N2 ambient is sometimes needed to improve the crystallize state of challecogenide material. The annealing temperature typically ranges 100 C to 400 C with an anneal time of less than 30 minutes.
The thickness of challecogenide material depends on the design of cell structure. In general, a challecogenide material with thickness of higher than 8 nm can have a phase change characterization so that the material exhibits at least two stable resistance states.
2. CMR (Colossal Magnetoresistance) Material
Or other compositions with x: 0˜1; y: 0˜1
Another CMR material that includes Mn oxide may be used
Formation method: By PVD sputtering or magnetron-sputtering method with reactive gases of Ar, N2, O2, and/or He, etc. at the pressure of 1 mtorr˜100 mtorr. The deposition temperature can range from room temperature to ˜600 C, depending on the post deposition treatment condition. A collimater with an aspect ratio of 1˜5 can be used to improve the fill-in performance. To improve the fill-in performance, the DC bias of several ten to several hundred volts is also used. On the other hand, the combination of DC bias and the collimater can be used simultaneously. A magnetic field of several ten gauss to 10,000 gauss may be applied to improve the magnetic crystallized phase
The thickness of CMR material depends on the design of cell structure. The CMR thickness of 10 nm to 200 nm can be used to be the core material.
3. 2-Element Compound
NixOy; TixOy; AlxOy; WxOy; ZnxOy; ZrxOy; CuxOy; etc
Other compositions with x: 0˜1; y: 0˜1
1. Deposition: By PVD sputtering or magnetron-sputtering method with reactive gases of Ar, N2, O2, and/or He, etc. at the pressure of 1 mtorr˜100 mtorr, using a target of metal oxide, such as NixOy; TixOy; AlxOy; WxOy; ZnxOy; ZrxOy; CuxOy; etc. The deposition is usually done at room temperature. A collimater with an aspect ratio of 1˜5 can be used to improve the fill-in performance. To improve the fill-in performance, the DC bias of several ten to several hundred volts is also used. If desired, they combination of DC bias and the collimater can be used simultaneously.
The post deposition annealing treatment with vacuum or N2 ambient or O2/N2 mixed ambient as sometimes needed to improve the oxygen distribution of metal oxide. The annealing temperature ranges 400 C to 600 C with an anneal time of less than 2 hours.
2. Reactive deposition: By PVD sputtering or magnetron-sputtering method with reactive gases of Ar/O2, Ar/N2/O2, pure O2, He/O2, He/N2/O2 etc. at the pressure of 1 mtorr˜100 mtorr, using a target of metal oxide, such as Ni, Ti, Al, W, Zn, Zr, or Cu etc. The deposition is usually done at room temperature. A collimater with an aspect ratio of 1˜5 can be used to improve the fill-in performance. To improve the fill-in performance, a DC bias of several ten to several hundred volts is also used. If desired, the combination of DC bias and the collimater can be used simultaneously.
3. Oxidation: By a high temperature oxidation system, such as furnace or RTP system. The temperature ranges from 200 C to 700 C with pure O2 or N2/O2 mixed gas at a pressure of several mtorr to 1 atm. The time can range several minute to hours. Another oxidation method is plasma oxidation. An RF or a DC source plasma with pure O2 or Ar/O2 mixed gas or Ar/N2/O2 mixed gas at a pressure of 1 mtorr to 100 mtorr is used to oxidize the surface of metal, such as Ni, Ti, Al, W, Zn, Zr, or Cu etc. The oxidation time ranges several seconds to several minutes. The oxidation temperature ranges room temperature to 300C, depending on the degree of plasma oxidation.
4. Polymer Material
TCNQ with doping of Cu, C60, Ag etc.
PCBM-TCNQ mixed polymer
1. Evaporation: By thermal evaporation, e-beam evaporation, or molecular beam epitaxy (MBE) system. A solid-state TCNQ and dopent pellets are co-evaporated in a single chamber. The solid-state TCNQ and dopent pellets are put in a W-boat or a Ta-boat or a ceramic boat. A high electrical current or an electron-beam is applied to melt the source so that the materials are mixed and deposited on wafers. There are no reactive chemistries or gases. The deposition is done at a pressure of 10-4 torr to 10-10 torr. The wafer temperature ranges from room temperature to 200 C.
2. Spin-coat: By a spin-coater with the doped-TCNQ solution @ the rotation of less than 1000 rpm. After spin-coating, the wafer is put to wait the solid-state formation @ room temperature or temperature of less than 200 C. The waiting time ranges from several minutes to days, depending on the temperature and on the formation conditions.
For additional information on the manufacture, component materials, use and operation of phase change random access memory devices, see U.S. patent application Ser. No. 11/155,067, filed 17 Jun. 2005, entitled Thin Film Fuse Phase Change Ram And Manufacturing Method.
The above descriptions may have used terms such as above, below, top, bottom, over, under, et cetera. These terms are used to aid understanding of the invention are not used in a limiting sense.
While the present invention is disclosed by reference to the preferred embodiments and examples detailed above, it is to be understood that these examples are intended in an illustrative rather than in a limiting sense. It is contemplated that modifications and combinations will occur to those skilled in the art, which modifications and combinations will be within the spirit of the invention and the scope of the following claims.
Any and all patents, patent applications and printed publications referred to above are hereby incorporated by reference.
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|U.S. Classification||257/295, 438/3, 257/E45.002|
|Cooperative Classification||H01L45/06, H01L45/145, H01L45/14, H01L45/144, H01L45/1253, H01L45/16, H01L45/1226, H01L45/146, H01L45/147|
|European Classification||H01L45/14, H01L45/14C4, H01L45/12D2, H01L45/14B6, H01L45/12E, H01L45/14C2, H01L45/16, H01L45/06|
|May 15, 2006||AS||Assignment|
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